Certain bactericidal triamine

ABSTRACT

A biocidal composition comprises a biocidally effective amount of a compound of the formula   wherein R H or C8H17, two of the R groups being C8H17, and an inert carrier, the pH of the composition being between about 5 to 8. A method for disinfecting with the biocidal composition is also disclosed.

United States Patent 1 Hofmann et a1.

[451 Oct. 14, 1975 Filed:

CERTAIN BACTERICIDAL TRIAIVIINE Inventors: Eberhard Hofmann,

Essen-Bredeney; Ulrich Holtschmidt, Essen, both of Germany Th. Goldschmidt AG, Essen, Germany Aug. 30, 1973 Appl. No.: 393,187

Related US. Application Data Continuation of Ser. No. 107,443, Jan. 18, 1971, abandoned.

Assignee:

Foreign Application Priority Data Feb. 27, 1970 Germany 2009276 US. Cl. 424/325; 252/107; 71/67 Int. Cl. A01N 9/20 Field of Search 424/325, 233

References Cited UNITED STATES PATENTS 5/1953 White et a1. 106/14 10/1963 Molnar 424/233 Primary Examiner-V. D. Turner Attorney, Agent, or Firm-Toren, McGeady and Stanger ABSTRACT A biocidal composition comprises a biocidally effective amount of a compound of the formula wherein R H or C 11 two of the R groups being C H and an inert carrier, the pH of the composition being between about 5 to 8.

A method for disinfecting with the composition is also disclosed.

biocidal 5 Claims, No Drawings 1' I CERTAIN BACTERICIDAL' TRIAMINE CROSS REFERENCE TO PRIOR DISCLOSURE This is a continuation of application Ser. No. 107,44 filed Jan. 18, 1971, and now abandoned. I

T F ELD O INVENTION The invention relates to the use of compounds of the foumula l wherein R H or C H two of the R groups being C H as biocides, particularly bactericides and fungicides.

BACKGROUND INFORMATION AND PRIOR ART The use of this starting product is indicated as particularly progressive.

SUMMARY OF THE INVENTlON It has now surprisingly been established that N- mono-octyldiethylenetriamine and N-monooctyldiethylenetriamino acetic acid do not exhibit any significant bactericidal characteristics in economincally feasible concentrations, while, by contrast, N-dioctyldiethylenetriamine constitutes a superior biocidally active substance, even in relatively small concentrations. The superior bactericidal characteristics of N-dioctyldiethylenetriamine are maintained in the presence of large amounts of protein, soap and the like. It has also been established that a composition containing the compound, to wit, N-dioctyldiethylenetriamine, is in its insensitivity in respect to protein and anionic detergents by far superior to the commercially available surface active cationic detergents such as quaternary ammonium compounds or ampholytic soaps.

The excellent bacteriological activity of the composition containing the compounds to be employed in accordance with this invention, is most surprising, because substances of homologue nature, such as, for example, dilauryldiethylenetriamine are, from a practical point of view, without bacteriological effect, while, by contrast, mono-lauryldiethylenetriamine demonstrates a significant initial bacteriological effect. However, the bacteriological effect of the latter compound is negatively affected by the presence of protein and anionic latter compound is by far inferior to a composition containing the compounds of this invention.

Surprisingly, it has also been established that the compound of the following formula II exhibits a significantly lesser bactericidal effect than the inventive comdetergents, so thatfrom a practical point of view, the i pounds, although the compound of formula 11 has the same gross formula.

In addition mm above mentioned advantages, compositions containing the inventive compounds are also superior in comparison with, for example, mono-alkyldiethylenetriamines, since, in the preparation of the inventive compounds, no large excess of a reaction partner is required. Rather, corresponding to the reaction formula, molar quantity ratios should be used. The cumbersome removal of the diethylenetriamine excess, .which is necessary in the preparation of mono-alkyldiethylenetriamine, is thus dispensed with in the preparation of the inventive compounds.

A still further advantage of the compounds to be used in the inventive composition resides in the fact that A 7 aqueous solutions of the compounds, which are pre- I pared with admixture of acids, do not have any significant tendency for foaming. By adding small amounts of non-ionogenic tensides,-a' strong-or weak foaming action can thus be adjusted at will. This, of course, is of great advantage for many applications. By contrast, in

the prior art quaternary ammonium compounds and ampholytic'soaps which have a strong foaming tendency, this can be accomplished only by the addition of large quantities of foam reducing agents, which makes the preparations uneconomical.

The compounds to be used in the inventive composition may be prepared in technically exceedingly simple manner by reaction of diethylenetriamine with, for example, n-octylchloride, n-octylbromide, 'or Di-noctylsulphate in a mole ratio of 1 lto l 4, preferably 1 l.5 to l 2.5,,in the presence-of acid acceptors and at temperatures of about to C.

A variety of acidacceptors may be used'for this purpose, for example, NaOH, KOH, Na CO K CO CaO,,

CaCO or the respective-[amine proper. The com-' pounds to be used in accordance withflthe invention may be isolated from the reaction mixture, for example, by distillation. However, distillation or other procedures resulting in isolation, are unnecessary if technical purity is sufficient forthe particular purpose.

For the purpose of preparing the inventive composition, the compounds aredissolved in 'a' suitable solvent, such as water, alcohols; glycolethers or mixtures thereof, with the addition of acids, which impart the final composition with a, pH-value'of about 5 8.

Suitable acids for this purpose are acetic acid, lactic acid, tartaric acid, citric acid, glucoriic acid, hydrochloric acid, phosphoric acid, and nitirc acid, the amount of acid to -be added being/such that the desired pH- value of from between 5 8 is attained.

With a view to regulating thefoaming behavior, nonionogenic tensides may be added, such as, for example,

the addition products of ethyleneoxide to laurylal affecting in any way the scope and spirit of the invention as recited in the appended claims.

EXAMPLE 1 Preparation of N-dioctyl-diethylenetriamine This experiment was carried out in a 2 liter threeneck flask fitted with stirrer, reflux cooler and thermometer. 2 mole of octylchloride, 1 mole of diethylenet'riamine, 5 ml of water and 2 mole of NaOH were added tothe flask and the mixture thus obtained was heated for 5 hours to a temperature of 130 to 140C. While still hot, the liquid was decanted from the inorganic residue, and the decanted liquid was subjected to fractional vacuum distillation. Diethylenetri'amine and mono-octyldiethylenetriamine were removed first by the distillation, whereafter, at a temperature of l30- l50C and a pressure of 0.2 to 1 mm Hg, 135 gram of pure N-dioctyldiethylenetriamine were recov ered.

Elementary Analysis Calculated for CmH N: (mole weight 327):

Found:

C 73.5% by weight H 1 l3.7% by weight N l2.8% by weight C 73.9% by weight H 13.9% by weight N 12.5% by weight EXAMPLE 2 parts by weight of N-dioctyl-diethylenetriamine, 10 parts by weight of an addition product of 12 mole of ethylene oxide to 1 mole of isotridecylalcohol, 10 parts by weight of acetic acid and 70 parts by weight of water are homogenized under stirring and heating to a temperature of about 50C. A yellow colored, clear and foaming solution was obtained which could be diluted with water to'a'ny desired extent.

EXAMPLE 3 was obtained which could be diluted with water to any desired extent.

EXAMPLE 5 A 50 parts by weight of N-dioctyl-diethylenetriamine, 25 parts by weight of an addition product of 20 mole of ethylene oxide tol mole of Iaurylalcohol, and 25 parts by weight of a mixed polymerisate of ethylene oxide and propylene oxide with a mole weight of 2000, as well as parts by weight of ethylglycol, were dissolved in 370 parts by weight of water. A clear. slightly foaming solution was obtained which could be diluted with water to any desired extent.

Bacteriological Investigations The investigation of the bacteriological characteristics was performed according to the Richtliniender Deutschen Gesellschaft fuer Hygiene rind Mikrobiologie (Guidelines of the German Association for Hygiene and Microbiology).

l. Bacteriological Activity of Diocctylethylenetriamine in Suspension Test tuted the inventive preparation.

20 parts by weight of N-dioctyl-diethylenetriamine,

30 parts by weight of an addition product of 15 mole of ethylene oxide to 1 mole of oleic acidmonoglyceride,

,20 parts by weight of lactic acid, and 20 parts by weight of ethylglycol, as well as 1 l0 parts by weight of water, were homogenizedunder stirring and heating to 40C. A clear, slightly foaming solution was obtained.

EXAMPLE 4 [n the following growth of bacteria no bacteria growth Action time in minutes I 2 5 X0 20 30 Species Concentration in Staphylo- CUL'CHS aureus llll llll

Pseudamonas aeruginosa Proteus 0.! vulgaris Escherichia 0. l (0 +lll llll

Illl

2. A composition was prepared in accordance with the invention which in addition to dioctyldiethylenetriamine contained the same amount by weight of a nonionogenic tenside, which had been obtained by reaction of 12 mole of ethylene oxide with 1 mole of isotridecylalcohol. The pH-value of the aqueous composition containing 0.1% of active substance was adjusted with acetic acid to 6.5.

-Continued Species Concentration in Action time in minutes pec e Concentration in Action time n minutes 1 2 5 2o 30 l 2 A 20 30 5 Siaphylo- 0.1 Psuedomonas 0.1 coccus Aerugi'nosa aureus 0.05 0.05 0.01 0.01

+ 'l' 'l p gleux o l l0 vulgaris Pseudomonas O.l 0.05 aerugi'nosa 0.01

0.05 0.01 Escherichia O.l 0.005 coIi 0.001 0.05 0.01

Proteus 0.1 v vulgaris 0.005 0.001 Exchen-chia OJ ll. Bacteriological Activity of Comparison Substances l. Bacteriolo ical activit of 0.05 I g y 0.01

C H NH-CH -CH -NH-CH --CH NH--C H v v (in suspension test) 3. Determinationof Soap Sensitivity 1 i An aq Solution was P p which contained Thepl-l valueof an aqueous solution containing 0.1% of dloctylethylenetl'lamme-v- The 5011111011 of the active substance was adjusted with acetic acid to tained additionally 0.1% of soft soap. .=The dilutions 6 5 were also admixed with 0.1% of soft soap. Species Concentration in Action time in minutes Species Concentration in Action time in minutes Staphylu- ,0.1 i Staphylu- O.l coccus caccus aureus 0.05 aureus I 0.05

, 0.005 Pseudor nonas 0.1

amgmosai 05 Pseudpmunas 0.1

0.01 0.05 Proteus OJ 0.01

vulgaris 0.01. Eschericliia 0.1 (L005 0.001

0.05 r- Escherichia 0.1

culi' 0.05 0.01 4. Determination of Protein Sensitivity (1005 An aqueous solution of dioctylethylenetriamine was 1 prepared in which all the examined dilution stages contained 20% of bovine serum.

Bacteriological Activity of y l 2. Lauryldiethyleneti'iamine and spews cmcem'amn g 'g 'l'a' g 3. Dilaurylethylenetriamine in suspension test The pH value of the aqueous preparation containing Staphylu- 0.1 e 0.1% of active compound and 0.1% of nonionogenic 0 05 tenside, was adjusted to 6.5. The non-ionogenic tenside was obtained by addition of 12 mole of ethylene oxide to 1 mole of isoti'idecylalcohol.

2) Action time in minutes Concentration Species Pseudomuna: aeruginora 3 Action time in minutes Proteus 0. l vulgaris Escherichia culi 4. Bacteriological Activity of C lgl, Nl-l cH -CH NHCH CH NH and Under the conditions of the suspension test, aqueous solutions of the above comparison compounds, at the same pH value as in the inventive compositions, do not exhibitany bacteriological effect. This applies to the comparison substances per se and also in the presence of non-ionogeriic tensides. i

5. The bacteriological effect of a commercially available quaternary ammonium compound (N-dimethyh alkyl-benzyl-ammonium-chloride) whose alkyrest consists to 50% by weight of a carbon chain with 14 atoms, to 40% by weight of a carbon chain with 12 carbon atoms, and by weight of a chain with 16 ,carbon atoms.

a. in the presence of 20% bovine serum b. in the presence of 0.1% potassium soap.

Comparison of the bacteriological activity of the inventive compositions, as they are listed-under 1.1 and 1.2 with that of the comparison substances according to ".1 through ".4, indicates clearly the superiority. of the inventive composition in the normal suspension test. The superiority of the inventive compounds under conditions simulating practical conditions, to wit, in the presence. of anionic detergents and proteins, is clear from the tests 1.3 and [.4 if compared with the prior art compounds as represented by the'quatemary ammonium compound according to ".5. It will be noted that the prior art compounds are much more sensitive than the inventive compounds.

We claim:

1. A method of inhibiting the growth of'bacteria, which comprises applying to the locus to be protected a bactericidal composition consisting essentially of a bactericidally effective amount of the compound N-dioctyl-diethylenetriamine and an acid in an amount sufficient to impart to the composition a pH value of between about 5 8, and an inert carrier.

Species Concentration Action time A ti i in in minutes v i mi Slap/zylo- O. l

coccus 1 nureus 0.05 g

Pseudomonus 0. l aeruginos Proteus 1 0.1

vulgaris I g Escherichia 0. 1 culi 5. A method of inhibiting the growth of bacteria, which comprises applying to the locus to be protected a bactericidal composition consisting essentially of a bactericidally effective amount of the compound N-dioctyl-diethylenetriamine, an acid in an amount sufficient to impart the composition a pH value of between 5 8, an inert carrier and a non-ionogenic tenside. 

1. A METHOD OF INHIBITING THE GROWTH OF BACTERIA, WHICH COMPRISES APPLYING TO THE LOCUS TO BE PROTECTED A BACTERICIDAL COMPOSITION APPLYING ESSENTIALLY OF A BACTERICIDALLY EFFECTIVE AMOUNT OF THE COMPOUND N-DIOCTY-DIETHYLENETRIAMINE AND AN ACID IN AN AMOUNT SUFFICIENT TO IMPART TO THE COMPOSITION A PH VALVE OF BETWEEN ABOUT 5-8, AND AN INERT CARRIER.
 2. A method as claimed in claim 1, wherein the acid is selected from the group consisting of acetic acid, hydrochloric acid, phosphoric acid, lactic acid, tartaric acid, citric acid, gluconic acid, and nitric acid.
 3. A method as claimed in claim 1, wherein said inert carrier is water, alcohol, ethyl ether of ethylene glycol or propylene glycol.
 4. A method as claimed in claim 1, wherein the concentration of said compound in the composition is between about 0.001 to 0.1 per cent by weight.
 5. A method of inhibiting the growth of bacteria, which comprises applying to the locus to be protected a bactericidal composition consisting essentially of a bactericidally effective amount of the compound N-dioctyl-diethylenetriamine, an acid in an amount sufficient to impart the composition a pH value of between 5 - 8, an inert carrier and a non-ionogenic tenside. 